EP0672688B1 - Aluminiumfreie Monocyclopentadienyl-Metallocenkatalysatoren für Olefinpolymerisation - Google Patents

Aluminiumfreie Monocyclopentadienyl-Metallocenkatalysatoren für Olefinpolymerisation Download PDF

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EP0672688B1
EP0672688B1 EP95200999A EP95200999A EP0672688B1 EP 0672688 B1 EP0672688 B1 EP 0672688B1 EP 95200999 A EP95200999 A EP 95200999A EP 95200999 A EP95200999 A EP 95200999A EP 0672688 B1 EP0672688 B1 EP 0672688B1
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substituted
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EP0672688B2 (de
EP0672688A1 (de
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Jo Ann Marie Canich
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ExxonMobil Chemical Patents Inc
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Exxon Chemical Patents Inc
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/72—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44
    • C08F4/74—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44 selected from refractory metals
    • C08F4/76—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44 selected from refractory metals selected from titanium, zirconium, hafnium, vanadium, niobium or tantalum
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F17/00—Metallocenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring

Definitions

  • This invention relates to a process using a catalyst system comprising certain transition metal compounds of the Group IV-B metals of the Periodic Table of Elements and an ion-exchange activator compound, for the production of polyolefins, particularly polyethylene, polypropylene, and ethylene- ⁇ -olefin copolymers.
  • EP 277003 and EP 277004 disclose ionic metallocene based catalysts obtainable from bis (cyclopentadienyl) derivatives of a Group IV-B metal compound and reagents which will irreversibly react with the Group IV-B metal compounds, and their use in polymerization of olefins.
  • EP 129368 discloses monocyclopentadienyl Group IV-B metal compounds which form catalysts with alumoxane, which Group IV-B compounds may have halo ligands and include no heteroatom ligand bonded through the heteroatom to the metal.
  • EP 250601 discloses catalysts of bis(cyclopentadienyl) derivatives of Group IV-B metals and alumoxane which include heteroatom ligands bonded through the heteroatom to the metal. Monocycopentadienyl compounds are referred to generically in the claims. EP 250601 does not disclose a cocatalyst other than alumoxane and does not disclose monocyclopentadienyl compounds having a bridge between the heteroatom and the cyclopentadienyl ring.
  • EP 418044 discloses catalysts comprising a monocyclopentadienyl or substituted monocyclopentadienyl metal complex containing compound corresponding to the formula: CpMX n + A - , wherein Cp is a single ⁇ 5 cyclopentadienyl or ⁇ 5 -substituted cyclopentadienyl group optionally covalently bonded to M through a substituent; M is a metal of Group IIIB, IVB, VB, VIB, VIII or the Lanthanide Series of the Periodic Table bound in an ⁇ 5 bonding mode to the cyclopentadienyl or substituted cyclopentadienyl group; X is independently each occurrence halo, alkyl, aryl, -NR 2 aroxy or alkoxy of up to 20 carbons, or two or more X groups together form a metallocycle with M; R is alkyl or aryl of up to 10 carbons; n is one or two depending
  • Example 1 uses pentamethyl cyclopentadienyl titanium isopropoxide dimethyl which contains a heteroatom in combination with an alkyl ligand.
  • the earliest priority document from which EP 418044 claims priority discloses polymerization processes using such catalysts to polymerize a lower ⁇ -olefin (having from 3 to 8 carbon atoms) only at a temperature within the range from 0°C to 100°C and at a pressure within the range from 100 kPa to 3400 kPa.
  • the invention seeks to provide a process for producing polyolefin that does not contain an undesirable amount of catalyst residue (or ash content, measured as the non-volatile aluminum and transition metal content).
  • Aluminum alkyl-free olefin polymerization catalysts derived from transition metal complexes containing fewer than two cyclopentadiene have been relatively unexplored.
  • John Bercaw reported [Organometallics, 1990, 9, 867] the synthesis of a monocyclopentadienyl scandium polymerization catalyst, [Me 2 Si(C 5 Me 4 ) (N-Bu t )ScH(PMe 3 ] 2 .
  • This neutral Group III catalyst has a low activity and is very expensive due to the high cost of scandium metal.
  • the catalyst is not a substituted monocyclopentadienyl metal complex containing compound corresponding to the formula: CpMX n + A - wherein Cp is a single ⁇ 5 -substituted cyclopentadienyl group covalently bonded to M through a substituent; X is alkyl, aryl or alkoxy of up to 20 carbons; and n is one.
  • Group IV-B transition metal component can be a polyalkyl or hydride complex containing fewer than two cyclopentadienyl groups.
  • the catalyst system is represented by the general formula: wherein: M is Zr, Hf or Ti and is in its highest formal oxidation state (+4, d 0 complex);
  • [A] - is a labile, bulky anion which is a single coordination complex having a plurality of lipophilic radicals covalently coordinated to and shielding a central charge-bearing metal or metalloid core and may be formed when the second component, an activator compound comprising a cation which will irreversibly react with at least one ligand contained in said Group IV-B metal compound and a noncoordinating anion [A] - , is combined with the Group IV-B transition metal component, or 'first component'.
  • the cation of the second component reacts with one of the ligands of the first component, thereby generating an ion pair consisting of a Group IV-B metal cation with a formal coordination number of 3 and a valence of +4 and the aforementioned anion, which anion is compatible with and non-coordinating toward the metal cation formed from the first component.
  • Illustrative but not limiting examples of cations of the second component include Bronsted acids such as ammonium ions or reducible Lewis acids such as Ag + or ferrocenium ions.
  • the anion of the second compound stabilizes the Group IV-B metal cation complex without interfering with the Group IV-B metal cation's or its decomposition product's ability to function as a catalyst and is sufficiently labile to permit displacement by an olefin, diolefin or an acetylenically unsaturated monomer during polymerization.
  • Catalyst systems of the invention may be prepared by placing the Group IV-B transition metal component and the ion-exchange component in common solution in a normally liquid alkane or aromatic solvent, which solvent is preferably suitable for use as a polymerization diluent for the liquid phase polymerization of an olefin monomer.
  • Suitable catalysts can also be prepared by reacting the components and adsorbing on a suitable support material (inorganic oxides or polymers, for example) or by allowing the components to react on such support.
  • the process of this invention is practiced with that class of ionic catalysts prepared by combining at least two components.
  • the first of these is a monocyclopentadienyl derivative of a Group IV-B metal compound containing at least one ligand which will combine with the second component or at least a portion thereof such as a cation portion thereof.
  • the second component is an activator, ion-exchange compound comprising a cation which will irreversibly react with at least one ligand contained in said Group IV-B metal compound and a bulky, labile anion which is normally non-coordinating and stable.
  • the cation of the second component reacts with one of the ligands of the first component, thereby generating an ion pair consisting of a Group IV-B metal cation with a formal coordination number of 3 and a valence of +4 and the aforementioned anion, which anion is compatible with and non-coordinating towards the metal cation formed from the first component.
  • the anion of the second compound stabilizes the Group IV-B metal cation complex without interfering with the Group IV-B metal cation's or its decomposition product's ability to function as a catalyst and is sufficiently labile to permit displacement by an olefin, diolefin or an acetylenically unsaturated monomer during polymerization.
  • the Group IV-B transition metal component of the catalyst system is represented by the general formula: wherein: M is Zr, Hf or Ti and is in its highest formal oxidation state (+4, d 0 complex);
  • Exemplary hydrocarbyl radicals for the Q are methyl, ethyl, propyl. butyl, amyl, isoamyl. hexyl, Isobutyl, heptyl, octyl, nonyl, decyl, cetyl, 2-ethylhexyl or phenyl, with methyl being preferred.
  • Exemplary substituted hydrocarbyl radicals include trifluoromethyl, pentafluorphenyl, trimethylsilylmethyl, and trimethoxysilylmethyl.
  • Exemplary hydrocarbyl substituted metalloid radicals include trimethylsilyl, trimethylgermyl or triphenylsilyl.
  • alkyldiene radicals for both Q together are methylidene, ethylidene and propylidene.
  • Q group which are suitable as a constituent group or element of the Group IV B transition metal component of the catalyst system are identified in Column 4 of Table 1 under the heading "Q".
  • Suitable hydrocarbyl and substituted hydrocarbyl radicals which may be substituted as an R group for at least one hydrogen atom in the cyclopentadienyl ring, will contain from 1 to 20 carbon atoms and include straight and branched alkyl radicals, cyclic hydrocarbon radicals, alkyl-substituted cyclic hydrocarbon radicals, aromatic radicals and alkyl-substituted aromatic radicals.
  • Suitable organometallic radicals which may be substituted as an R group for at least one hydrogen atom in the cyclopentadienyl ring, include trimethylsilyl, triethylsilyl, ethyldimethylsilyl, methyldiethylsilyl, triphenylgermyl and trimethylgermyl.
  • Examples of cyclopentadienyl ring groups (C 5 H 5-y-x R x ) which are suitable as a constituent group of the Group IV-B transition metal component of the catalyst system are identified in Column 2 of Table 1 under the heading (C 5 H 5-y-x R x ).
  • Suitable hydrocarbyl and substituted hydrocarbyl radicals which may be substituted as an R' group for at least one hydrogen atom in the heteroatom J ligand group, will contain from 1 to 20 carbon atoms and include straight and branched alkyl radicals, cyclic hydrocarbon radicals, alkyl-substituted cyclic hydrocarbon radicals, aromatic radicals and alkyl-substituted aromatic radicals.
  • heteroatom ligand groups JR' z-l-y
  • heteroatom ligand groups which are suitable as a constituent group of the Group IV B transition metal component of the catalyst system are identified in Column 3 of Table 1 under the heading (JR' z-l-y ).
  • Table 1 depicts representative constituent moieties for the "Group IV-B transition metal component", the list is for illustrative purposes only and should not be construed to be limiting in any way. A number of final components may be formed by permuting all possible combinations of the constituent moieties with each other.
  • Illustrative compounds are: dimethylsilyltetramethylcyclopentadienyl- tert -butylamido zirconium dimethyl, dimethylsilyltetramethylcyclopentadienyl- tert -butylamido hafnium diethyl, dimethylsilyl- tert -butylcyclopentadienyl- tert -butylamido zirconium dihydride, dimethylsilyl- tert -butylcyclopentadienyl- tert -butylamido hafnium diphenyl, dimethylsilyltrimethylsilylcydopentadienyl- tert -butylamido zirconium dihydride, dimethylsilyltetramethylcydopentadienylphenylamido titanium dimethyl, dimethylsilyltetramethylcyclopentadienylphenylamido hafn
  • the above compounds and those permuted from Table 1 do not include the neutral Lewis base ligand (L).
  • the conditions under which complexes containing neutral Lewis base ligands such as ether or those which form dimers is determined by the steric bulk of the ligands about the metal center.
  • a preferred method of preparing these compounds is by reacting a cyclopentadienyl lithium compound with a dihalo-compound whereupon a lithium halide salt is liberated and a monohalo substituent becomes covalently bound to the cyclopentadienyl compound.
  • the so substituted cyclopentadienyl reaction product is next reacted with a lithium salt of a phosphide, oxide, sulfide or amide (for the sake of illustration, a lithium amide) whereupon the halo element of the monohalo substituent group of the reaction product reacts to liberate a lithium halide salt and the amine moiety of the lithium amide salt becomes covalently bound to the substituent of the cyclopentadienyl reaction product.
  • a lithium salt of a phosphide, oxide, sulfide or amide for the sake of illustration, a lithium amide
  • the resulting amine derivative of the cyclopentadienyl product is then reacted with an alkyl lithium reagent whereupon the labile hydrogen atoms, at the carbon atom of the cyclopentadienyl compound and at the nitrogen atom of the amine moiety covalently bound to the substituent group, react with the alkyl of the lithium alkyl reagent to liberate the alkane and produce a dilithtum salt of the cyclopentadienyl compound.
  • the bridged species of the Group IV-B transition metal compound is produced by reacting the dilithium salt cyclopentadienyl compound with a Group IV-B transition metal preferably a Group IV-B transition metal halide.
  • Unbridged species of the Group IV-B transition metal compound can be prepared from the reaction of a cyclopentadienyl lithium compound and a lithium salt of an amine with a Group IV-B transition metal halide.
  • bridged Group IV B transition metal compounds examples include dimethylsilyl, methylphenylsilyl, diethylsilyl, ethylphenylsilyl, diphenylsilyl, ethylene or methylene bridged compounds. Most preferred of the bridged species are dimethylsilyl, diethylsilyl and methylphenylsilyl bridged compounds.
  • Compounds useful as an activator component in the preparation of the catalyst used in the process of this invention will comprise a cation, which may be a Bronsted acid capable of donating a proton, and an anion which is normally compatible, noncoordinating, bulky, capable of stabilizing the active catalyst species (the Group IV-B cation) which is formed when the two compounds are combined and which is sufficiently labile to be displaced by olefinic, diolefinic and acetylenically unsaturated substrates or other neutral Lewis bases such as ethers. nitriles and the like.
  • Such compatible non-coordinating anions have been disclosed in our European Patent Application 277,004: anionic single coordination complexes comprising a plurality of lipophilic radicals covalently coordinated to and shielding a central charge-bearing metal or metalloid core.
  • activator compounds containing single anionic coordination complexes which are useful in this invention may be represented by the following general formula: 5. [(L'-H) + ] d [(M') m+ Q 1 Q 2 ...Q n ] d- wherein:
  • any metal or metalloid capable of forming an anionic complex which is stable in water may be used or contained in the anion of the second compound.
  • Suitable metals include, but are not limited to, aluminum, gold and platinum.
  • Suitable metalloids include, but are not limited to, boron, phosphorus and silicon.
  • Compounds containing anions which comprise coordination complexes containing a single metal or metalloid atom are, of course, well known and many, particularly such compounds containing a single boron atom in the anion portion, are available commercially. In light of this, salts containing anions comprising a coordination complex containing a single boron atom are preferred.
  • the preferred activator compounds comprising boron may be represented by the following general formula: 5A. [(L'-H) + [BAr 1 Ar 2 X 3 X 4 ] - wherein:
  • Ar 1 and Ar 2 may, independently, be any aromatic or substituted-aromatic hydrocarbon radical containing from 6 to 20 carbon atoms.
  • Suitable aromatic radicals include, but are not limited to, phenyl. naphthyl and anthracenyl radicals.
  • Suitable substituents on the substituted-aromatic hydrocarbon radicals include, but are not necessarily limited to, hydrocarbyl radicals, organometalloid radicals, alkoxy radicals, alkylamido radicals, fluoro and fluorohydrocarbyl radicals such as those useful as X 3 and X4.
  • the substituent may be ortho, meta or para, relative to the carbon atoms bonded to the boron atom.
  • each may be the same or a different aromatic or substituted-aromatic radical as are Ar 1 and Ar 2 , or the same may be a straight or branched alkyl, alkenyl or alkynyl radical having from 1 to 20 carbon atoms, a cyclic hydrocarbon radical having from 5 to 8 carbon atoms or an alkyl-substituted cyclic hydrocarbon radical having from 6 to 20 carbon atoms.
  • X 3 and X 4 may also, independently, be alkoxy or dialkylamido radicals wherein the alkyl portion of said alkoxy and dialkylamido radicals contain from 1 to 20 carbon atoms, hydrocarbyl radicals and organometalloid radicals having from 1 to 20 carbon atoms.
  • Ar 1 and Ar 2 may be linked to each other.
  • either or both of Ar 1 and Ar 2 could be linked to either X 3 or X 4 .
  • X 3 or X 4 may also be linked to each other through a suitable bridging group.
  • the catalyst systems employed in the process of the invention comprise a complex formed upon admixture of the Group IV-B transition metal component with the activator component.
  • the catalyst system may be prepared by addition of the requisite Group IV-B transition metal and activator components to an inert solvent in which olefin polymerization can be carried out by a solution polymerization procedure.
  • the catalyst system may be conveniently prepared by placing the selected Group IV-B transition metal component and the selected activator component, in any order of addition, in an alkane or aromatic hydrocarbon solvent -- preferably toluene.
  • the catalyst system may be separately prepared, in concentrated form, and added to the polymerization diluent in a reactor.
  • the components of the catalyst system may be prepared as separate solutions and added to the polymerization diluent in a reactor, in appropriate ratios, as is suitable for a continuous liquid polymerization reaction procedure.
  • Alkane and aromatic hydrocarbons suitable as solvents for formation of the catalyst system and also as a polymerization diluent are exemplified by, but are not necessarily limited to, straight and branched chain hydrocarbons such as isobutene, butane, pentane, hexane, heptane and octane, cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane and methylcycloheptane, and aromatic and alkyl-substituted aromatic compounds such as benzene, toluene and xylene.
  • Suitable solvents also include liquid olefins which may act as monomers or comonomers including ethylene, propylene, butene and 1-hexene.
  • the Group IV-B transition metal compound is present in the polymerization diluent in concentration of from 0.01 to 1.0 millimoles/liter of diluent and the activator component is present in an amount to provide a molar ratio of the transition metal to activator component from 1:1 to 200:1.
  • Sufficient solvent should be employed so as to provide adequate heat transfer away from the catalyst components during reaction and to permit good mixing.
  • the catalyst system ingredients that is, the Group IV-B transition metal and activator components, and polymerization diluent can be added to the reaction vessel rapidly or slowly.
  • the temperature maintained during the contact of the catalyst components can vary widely, such as, for example, from -10° to 300°C. Greater or lesser temperatures can also be employed.
  • the reaction is maintained within is a temperature of from 25° to 100°C, most preferably 25°C.
  • the individual catalyst system components, as well as the catalyst system once formed are protected from oxygen and moisture. Therefore, the reactions are performed in an oxygen and moisture free atmosphere and, where the catalyst system is recovered separately, it is recovered in an oxygen and moisture free atmosphere. Preferably, therefore, the reactions are performed in the presence of an inert dry gas such as, for example, helium or nitrogen.
  • an inert dry gas such as, for example, helium or nitrogen.
  • the overall catalytic performance of the catalyst depends on the choice of metal, the specific (CN)-ligand set, the structure and stability of A-, and the coordinating ability of the cation or Lewis base L'.
  • the cation is a proton donor and the Q-ligand of the transition metal component is chosen so that: 1) the metal complex is easy to prepare and is low cost; 2) (CN)MQ 2 is sufficiently basic to deprotonate the acidic cation of the activator component; and 3) Q-H is an unreactive biproduct such as an alkane so that the activation reaction is irreversible.
  • the L' and A - portions of the activator component "tune" the stability and overall performance of the catalyst system.
  • L' and A - to modify the behavior of a catalyst site increases the versatility of the polymerization system which is an important advantage over conventional methods of activation (e.g. methylalumoxane, and other aluminum alkyl cocatalysts).
  • transition metal components identified above may be combined with most activator components identified above to produce an active olefin polymerization catalyst, it is important for continuity of the polymerization operations that either the metal cation initially formed from the first component or a decomposition product thereof be stable. It is also important that the anion of the activator compound be stable to hydrolysis when an ammonium salt is used. Further, it is important that the positive charge of the activator component be sufficient, relative to the metal component, to facilitate the needed cation, e.g., proton transfer. Activator compounds containing aryl-ammonium salts such as N,N-dimethylantlium are more acidic than trialkylammonium salts and therefore are useful with a wider variety of transition metal components. The basicity of the metal complex must also be sufficient to facilitate the needed proton transfer. In general, transition metal compounds which can be hydrolysed by aqueous solutions can be considered suitable as metallocene components to form the catalysts described herein.
  • the two compounds combined for preparation of the active catalyst must be selected so as to avoid transfer of a fragment of the anion to the metal cation, thereby forming a catalytically inactive species. This could be done by steric hindrance, resulting from substitutions on the Cp- and/or J-ligands of the first component, as well as substitutions on the non-coordinating anion.
  • non-coordinating anion is an anionic coordination complex, such as a tetraphenylboron derivative
  • substitutions on the phenyl rings can be used to prevent the transfer of a proton or an entire phenyl group from the anion to the metal. This can be accomplished by alkyl substitution in the ortho positions of the phenyl groups, or, more preferably, by perfluoro-substitutions on the anion.
  • anionic coordination complexes containing perfluorophenyl-, trifluoromethylphenyl-, or bis-trifluormethylphenyl rings are preferred for this subgenus of activator components.
  • the NMR data clearly suggest that the amine is indeed coordinated to the zirconium atom, but that it is fluxional and probably has two orientations of coordination, most likely in the form of rotational isomers.
  • the ionic catalysts species can be crystallized out at -40°C giving a pale powder.
  • the solid state NMR spectrum of this material revealed amine coordination to the zirconium atom with more than one orientation.
  • the catalyst system is utilized in a liquid phase polymerization of an olefin monomer.
  • the liquid phase process comprises the steps of contacting an olefin monomer with the catalyst system in a suitable polymerization diluent and reacting said monomer in the presence of said catalyst system for a time and at a temperature sufficient to produce a polyolefin.
  • the monomer for such process may comprise ethylene alone, for the production of a homopolyethylene, or ethylene in combination with an ⁇ -olefin having 3 to 18 carbon atoms for the production of an ethylene- ⁇ -olefin copolymer.
  • Conditions for the homo- or copolymerization of ethylene are those wherein ethylene is submitted to the reaction zone at pressures of from 0.0013 bar (0.019 psi) to 3445 bar (50,000 psi) and the reaction temperature is maintained at from -100°C to 300°C, preferably -10° to 220°C, with the proviso that when used to polymerize a lower ⁇ -olefin having from 3 to 8 carbon atoms at a temperature within the range from 0°C to 100°C and at a pressure within the range from 100 kPa to 3400 kPa, the catalyst is not a substituted monocyclopentadienyl metal complex containing compound corresponding to the formula: CpMX n + A - wherein Cp is a single ⁇ 5 -substituted cyclpentadienyl group covalently bonded to M through a substituent; X is alkyl or alkoxy of up to 20 carbons; and n is one.
  • one means for carrying out the process of the present invention is as follows: in a stirred-tank reactor liquid 1-butene monomer is introduced.
  • the catalyst system is introduced via nozzles in either the vapor or liquid phase.
  • Feed ethylene gas is introduced either into the vapor phase of the reactor, or sparged into the liquid phase as is well known in the art.
  • the reactor contains a liquid phase composed substantially of liquid 1-butene together with dissolved ethylene gas, and a vapor phase containing vapors of all monomers.
  • the reactor temperature and pressure may be controlled via reflux of vaporizing ⁇ -olefin monomer (autorefrigeration), as well as by cooling coils, jackets, etc.
  • the polymerization rate is controlled by the rate of catalyst addition, or by the concentration of catalyst.
  • the ethylene content of the polymer product is determined by the ratio of ethylene to 1-butene in the reactor, which is controlled by manipulating the relative feed rates of these components to the reactor.
  • lithiated substituted cyclopentadienyl compounds are typically prepared from the corresponding cyclopentadienyl ligand and BuLi or MeLi, or by reaction of MeLi with the proper solvene.
  • ZrCl 4 and HfCl 4 were purchased from either Aldrich Chemical Company or Cerac.
  • Amines, silane and lithium reagents were purchased from Aldrich Chemical Company or Petrarch Systems.
  • Activator components were prepared by known literature methods.
  • Me 2 Si(Me 4 C 5 )(N- t -Bu)ZrCl 2 (1.07 g, 0.0026 mole) was recovered. Additional Me 2 Si(Me 4 C 5 )(N- t -Bu)ZrCl 2 was recovered from the filtrate by repeating the recrystallization procedure. Total yield, 1.94 g, 0.0047 mol).
  • Me 2 Si(C 5 Me 4 )(N- t -Bu)ZrMe 2 was prepared by adding a stoichiometric amound of MeLi (1.4 M in ether) to Me 2 Si(C 5 Me 4 )(N- t -Bu)ZrCl 2 suspended in ether. The white solid was isolated in an 83% yield.
  • MePhSiCl 2 (14.9 g, 0.078 mol) was diluted with ⁇ 250 ml of thf.
  • Me 4 C 5 HLi (10.0 g. 0.078 mol) was slowly added as a solid.
  • the reaction solution was allowed to stir overnight.
  • the solvent was removed via a vacuum to a cold trap held at -196°C. Petroleum ether was added to precipitate out the LiCl.
  • the mixture was filtered through Celite, and the pentane was removed from the filtrate.
  • MePhSi(Me 4 C 5 H)Cl (20.8 g, 0.075 mol) was isolated as a yellow viscous liquid.
  • MePhSi(Me 4 C 5 )(N- t -Bu)HfMe 2 was prepared by adding a stoichiometric amount of HeLi (1.4 M in ether) to MePhSi(Me 4 C 5 )(N- t -Bu)HfCl 2 suspended in ether. The white solid could be isolated in near quantitative yield.
  • a catalyst solution prepared from 19.7 mg of Me 2 Si(Me 4 C 5 )(N- t -Bu)ZrMe 2 and 6 mg of [DMAH] [B(pfp) 4 ] in 20 mls of toluene was added to a 1 liter stainless-steel autoclave containing 400 mls of hexane.
  • the reactor temperature was maintained at 40°C and stirred vigorously while ethylene was added at 6.2 bar (90 psi). After 30 minutes the reaction was stopped giving 30 grams of HDPE after work-up.
  • the GPC analysis showed a bimodal distribution with modes centered at 900,000 and 2,000.
  • a catalyst solution prepared from 28.6 mg of Me 2 Si(Me 4 C 5 )(N- t -Bu)ZrMe 2 and 9 mg of [DMAH] [B(pfp)] 4 in 20 mls of toluene was added to a 1 liter stainless-steel autoclave containing 400 mls of hexane.
  • the reactor temperature was set at 50°C and was stirred vigorously while 100 mls of butene and 4.1 bar (60 psi) of ethylene were added. Following the addition of butene and ethylene, an instantaneous increase in temperature to 90°C was observed. After 30 minutes the reaction was stopped, yielding 130 grams of a waxy ethylene-butene copolymer.
  • GPC analysis showed a bimodal distribution with modes centered at 27,000 and 2,000 in approximately equal ratios.
  • IR spectroscope showed the presence of butene in the copolymer.
  • a catalyst solution prepared from 40 mg of MePhSi(C 5 Me 4 )(N- t -Bu)HfMe 2 and 11 mg of [DMAH][B(pfp 4 ] in 20 mls of toluene was added to a 1 liter autoclave containing 400 mls of hexane.
  • the reactor temperature was set at 40°C, stirred vigorously and pressurized with ethylene 4.1 bar (90 psi) for 15 minutes.
  • the reactor temperature increased from 40 to 97°C during the polymerization.

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Claims (16)

  1. Verfahren zur Homo- oder Copolymerisation von Ethylen, bei dem Ethylen einer Reaktionszone mit einem Druck von 0,0013 bar bis 3445 bar und einer Temperatur von -100 bis 300°C zugeführt wird, wobei ein Katalysatorsystem mit der folgenden Formel verwendet wird
    Figure imgb0008
        in der M Zr, Hf oder Ti ist und in seiner höchsten formalen Oxidationsstufe (+4, d0-Komplex) vorliegt,
    (C5H5-y-xRx) ein Cyclopentadienylring ist, der mit null bis fünf Substituentengruppen R substituiert ist, "x" 0, 1, 2, 3, 4 oder 5 ist und den Substitutionsgrad bezeichnet und jede Substituentengruppe R unabhängig ein Rest ausgewählt aus einer Gruppe bestehend aus C1- bis C20-Kohlenwasserstoffresten, substituierten C1- bis C20-Kohlenwasserstoffresten, bei denen ein oder mehrere Wasserstoffatome durch ein Halogenatom ersetzt sind, mit C1- bis C20-Kohlenwasserstoff substituierten Metalloidresten, bei denen das Metalloid ausgewählt ist aus der Gruppe IV A des Periodensystems der Elemente, und Halogenresten ist, oder (C5H5-y-xRx) ein Cyclopentadienylring ist, in dem zwei benachbarte R-Gruppen unter Bildung eines C4- bis C20-Rings verbunden sind, um einen polycyclischen Cyclopentadienylliganden zu ergeben;
    (JR'z-l-y) ein Heteroatomligand ist, in dem J ein Element mit einer Koordinationszahl von drei aus der Gruppe V-A oder ein Element mit einer Koordinationszahl von zwei aus der Gruppe VI-A des Periodensystems der Elemente ist und jedes R' unabhängig ein Rest ausgewählt aus einer Gruppe bestehend aus C1- bis C20-Kohlenwasserstoffresten und substituierten C1- bis C20-Kohlenwasserstoffresten, in denen ein oder mehrere Wasserstoffatome durch ein Halogenatom ersetzt sind, ist, und "z" die Koordinationszahl des Elements J ist,
    jedes Q unabhängig Hydrid, C1- bis C50-Kohlenwasserstoffreste, substituierte Kohlenwasserstoffreste, in denen ein oder mehrere Wasserstoffatome durch eine elektronenanziehende Gruppe wie ein Halogenatom oder einen Alkoxidrest ersetzt sind, oder mit C1- bis C50-Kohlenwasserstoff substituierte Metalloidreste sein kann, in denen das Metalloid ausgewählt ist aus der Gruppe IV-A des Periodensystems der Elemente mit der Maßgabe, daß, wenn irgendein Q ein Kohlenwasserstoff ist, dieses Q sich von (C5H5-y-xRx) unterscheidet, oder beide Q zusammen ein Alkyliden, Olefin, Acetylen oder cyclometallierter Kohlenwasserstoffrest sein können,
    "y" 0 oder 1 ist; wenn "y" 1 ist, B eine kovalente Brückengruppe ist, die ein Gruppe-IV-A- oder -V-A-Element enthält,
    L eine neutrale Lewisbase ist und "w" eine Zahl von 0 bis 3 ist, und
    [A]- ein labiles raumerfüllendes Anion ist, das ein einziger Koordinationskomplex mit mehreren lipophilen Resten ist, die kovalent um ein ladungstragendes Metall- oder Metalloidrentrum koordiniert sind und dieses abschirmen, mit der Maßgabe, daß bei Verwendung zum Polymerisieren eines niedrigeren α-olefins mit 3 bis 8 Kohlenstoffatomen bei einer Temperatur im Bereich von 0°C bis 100°C und einem Druck im Bereich von 100 kPa bis 3400 kPa der Katalysator kein substituierter Monocyclopentadienyl-Metall-Komplex ist, der eine Verbindung entsprechend der Formel CpMXn +A- enthält, in der Cp eine einzige η5-substituierte Cyclopentadienylgruppe ist, die über einen Substituenten kovalent an M gebunden ist, X Alkyl, Aryl oder Alkoxy mit bis zu 20 Kohlenstoffatomen ist und n eins ist.
  2. Verfahren nach Anspruch 1, in dem das Katalysatorsystem getrennt in konzentrierter Form hergestellt und einem Polymerisationsverdünnungsmittel zugegeben wird, oder bei dem das katalysatorsystem in situ in einem Polymerisationsverdünnungsmittel in dem Reaktor gebildet wird.
  3. Verfahren nach Anspruch 1, bei dem das Katalysatorsystem auf einem Träger adsorbiert ist.
  4. Verfahren nach Anspruch 1, bei dem in Stufen Ethylen entweder allein oder in Kombination mit anderen Olefinen und/oder anderen ungesättigten Monomeren in einem geeigneten Polymerisationsverdünnungsmittel mit dem Katalysatorsystem kontaktiert wird.
  5. Verfahren nach Anspruch 2, bei dem die Reaktionstemperatur auf -10 bis 220°C gehalten wird.
  6. Verfahren nach Anspruch 1, bei dem die Polymerisation in der flüssigen Phase erfolgt.
  7. Verfahren nach einem der Ansprüche 1 bis 6, bei dem das Element der Heteroatomligandengruppe Stickstoff, Phosphor, Sauerstoff oder Schwefel ist.
  8. Verfahren nach Anspruch 7, bei dem y=1 ist und B eine lineare, verzweigte oder cyclische Alkylengruppe mit 1 bis 6 Kohlenstoffatomen, eine alkylsubstituierte Silaalkylengruppe mit 1 bis 2 Siliciumatomen anstelle der Kohlenstoffatome in der Brücke oder eine Si1-Si2-alkylsubstituierte Silanylengruppe ist.
  9. Verfahren nach einem der vorhergehenden Ansprüche 1 bis 8, bei dem R' 1 bis 20 Kohlenstoffatome enthält und ein geradkettiger oder verzweigter Alkylrest, cyclischer Kohlenwasserstoffrest, alkylsubstituierter cyclischer Kohlenwasserstoffrest, aromatischer Rest oder ein alkylsubstituierter aromatischer Rest ist.
  10. Verfahren nach einem der vorhergehenden Ansprüche 1 bis 9, bei dem das Anion substituierte Phenylringe enthält, vorzugsweise einen ortho-alkylsubstituierten Phenylring, oder ein perfluorsubstituiertes Anion ist.
  11. Verfahren nach einem der vorhergehenden Ansprüche 1 bis 10, das während einer Zeitdauer von 1 Sekunde bis 10 Stunden durchgeführt wird, um ein Polymer mit einem durchschnittlichen Molekulargewicht (Gewichtsmittel) von 1000 bis 5 000 000 und einer Molekulargewichtsverteilung von 1,5 oder höher zu ergeben.
  12. Verfahren nach Anspruch 1, bei dem C5H5-y-xRx Tetramethylcyclopentadienyl ist.
  13. Verfahren nach Anspruch 1, bei dem Y=1 ist und B Dimethylsilyl ist.
  14. Verfahren nach Anspruch 1, bei dem JR'Z-1-y tert.-Butylamid ist.
  15. Verfahren nach Anspruch 1, bei dem Q Methyl ist.
  16. Verfahren nach Anspruch 1, bei dem M Titan ist.
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DE551277T1 (de) 1996-10-10
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ES2092913T3 (es) 1996-12-01
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EP0672688B2 (de) 2002-04-17
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